J. Coat. Technol. Res.
, 16 (3) 835–845, 2019
https://doi.org/10.1007/s11998-018-00156-4
Synergistic effect of Ag and ZnO nanoparticles on polyaniline
incorporated epoxy/2pack coatings for splash zone applications
Mohammad Asif Alam, Ubair Abdus Samad, El-Sayed M. Sherif, Asiful Seikh, Saeed M. Al-Zahrani,
Nabeel H. Alharthi, Manawwar Alam
 American Coatings Association 2018
Abstract In this work, epoxy/2pack coatings contain-
ing polyaniline (PANI) in combination with Ag and
ZnO nanoparticles have been synthesized. The
nanoparticles were incorporated with bisphenol-A
diglycidyl ether epoxy resin and polyamino-amide.
The mechanical properties of the fabricated coatings,
such as the pendulum hardness, scratch resistance, and
impact strength, were studied. The composition of the
fabricated coatings was confirmed by attenuated total
reflectance infrared spectroscopy measurements. The
thermal degradation and indentations were character-
ized through the use of differential scanning calorime-
try and nano-indentation techniques, respectively. The
surface morphology of the fabricated coatings was
characterized using field-emission scanning electron
microscopy. The synergistic effects of the Ag and ZnO
nanoparticles on the corrosion resistance of the coat-
ings after different exposure periods in 3.5% NaCl
solutions were determined by electrochemical impe-
dance spectroscopy. All the results were consistent
M. A. Alam (&), U. A. Samad, E.-S. M. Sherif,
A. Seikh, S. M. Al-Zahrani, N. H. Alharthi
Center of Excellence for Research in Engineering Materials
(CEREM), King Saud University, P. O. Box 800,
Riyadh 11421, Saudi Arabia
e-mail: moalam@ksu.edu.sa
E.-S. M. Sherif
Electrochemistry and Corrosion Laboratory, Department of
Physical Chemistry, National Research Centre, El-Behoth
St. 33, Dokki, Cairo 12622, Egypt
S. M. Al-Zahrani
Chemical Engineering Department, King Saud University,
P.O. Box 800, Riyadh 11421, Saudi Arabia
M. Alam (&)
Department of Chemistry, College of Science, King Saud
University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
e-mail: malamiitd@gmail.com
with one another and confirmed that the addition of
Ag and ZnO nanoparticles improved the mechanical
properties of the coatings. This effect also led to a
notable increase in the corrosion resistance of the
PANI coatings.
Keywords Epoxy coatings, Polyaniline,
Nanoparticles, Nano-indentation, Corrosion resistance,
Surface morphology
Introduction
Among electrically conducting polymers, polyaniline
(PANI) has the potential to emerge as the most
efficient corrosion-inhibiting pigment.1 This polymer
can be used to achieve high conductivity, and is
stable for various applications.2,3 Thin conducting films
can be coated with the help of PANI, resulting in an
improved adhesion on the substrate, and a stable sys-
tem can be achieved using the base materials.4,5
Therefore, PANI can substitute other corrosive and
hazardous inhibiting pigments in various organic coat-
ings, and impart better corrosion-inhibiting properties
as compared to conventional paint formulations. Thus,
this material can be incorporated and its performance
in other organic or epoxy coatings examined to ensure
the elimination of hazardous corrosion-inhibiting pig-
ments presently used in coatings; in addition, its effect
on the other properties of coating formulations can be
elucidated.4–6
The effects of PANI on the coating formulation can
be investigated through the incorporation with resin
and other paint ingredients. The composition of the
formulation after curing, which consists of a binder and
other additives and pigments, produces a hard and
durable film on the substrate. For this reason, PANI
has been used along with all of the additives and
ingredients of the formulation,7–9 the compositions of
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J. Coat. Technol. Res., 16 (3) 835–845, 2019
which affect the properties of this conducting polymer,
and can be investigated through different techniques to
establish the role of PANI in the final coating formu-
lation. Chen and Liu7 reported a novel approach to the
development of PANI-containing coatings with water-
borne corrosion protection through the preparation of
spherical PANI/partially phosphorylated poly(vinyl
alcohol) (PANI/P-PVA) nanoparticles using chemical
oxidative dispersion polymerization in the presence of
P-PVA. The authors7 also reported the corrosion
protection property of PANI/P-PVA-containing coat-
ings on mild steel using salt spray test and the EIS
method in a 3.0 wt% NaCl solution. Along with PANI,
the inorganic pigments also had a vital effect. There-
fore, it has become essential to study the impact of the
inorganic pigments in the coating composition along
with the polyaniline conducting polymer.8–10 The
incorporation of a PANI pigment with other inorganic
corrosion-inhibiting pigments has been reported to
provide corrosion-resistant properties in the coatings.
The intention of such incorporation was to observe the
effects of synergism of PANI and other species such as
Zn3(PO4)2.2H2O inorganic pigments.10 Different coat-
ing formulations based on PANI and inorganic anti-
corrosive pigments have been developed to investigate
the anticorrosion and adhesion properties of formu-
lated coatings. The incorporation of PANI and Zn-
powder, which is an electrochemically active pigment
in the coating formulation, has been characterized and
investigated to prove the synergism and anticorrosion
efficiency of the coating system.11
The conductivity and thermal and electrochemical
properties can be enhanced through the incorporation
of different types of nanomaterials along with the
PANI conducting polymer. Many materials can be
used, including graphite, TiO2, ZnO, ZrO2, and SiO2
nanoparticles.12–15 In particular, ZnO, ZrO2, and SiO2
have been reported in a previously published article16
as having increased the corrosion efficiency of the
coating. The total effect or improvement may be
associated with the strong bonding between inorganic
and organic phases, as well as the interaction with the
nanoparticles and PANI, which is expected to increase
the mechanical and electrical properties of the
nanocomposite produced.15 The author attempted for
the first time to produce PANI-based nanocomposites
with the incorporation of inorganic nanoparticles of
TiO2, Ag, and Zn through the specific and well-known
chemical vapor deposition method. The prepared
coatings were investigated using corrosion resistance
measurements, and the performances of various
nanocomposites were compared. The results exhibited
an enhancement in the corrosion protection efficiency
of Ag-incorporated nano-coatings, which motivated
our research towards the development of epoxy-
matrix-based formulations.
We prepared different nanocomposites based on
nano-pigments, Ag, TiO2, and ZnO, with the incorpo-
ration of a polyaniline conducting polymer (PANI).15
The corrosion behaviors of PANI, PANI/TiO2, PANI/
836
Ag, and PANI/Zn nanocomposite films were studied in
a 3.5% NaCl solution. The comparison results were
obtained by applying the Tafel extrapolation and EIS
techniques. The findings indicate that PANI/Ag
nanocomposite films yielded a higher protection
efficiency (PE = 97.54%) compared to PANI
(PE = 91.41%), PANI/TiO2 (PE = 91.91%), and
PANI/Zn (PE = 92.52%) nanocomposite films.14 The
results show that the addition of nanomaterials (TiO2,
Ag, and Zn) into the polymer matrix of PANI
enhanced the electrical conductivity of the PANI/Zn
film and the corrosion resistance of the polyaniline
polymer. These findings were further confirmed
through a decrease in the oxygen and water perme-
ability, and an increase in the coating adhesion in the
presence of TiO2, Ag, and Zn nanomaterials, in the
PANI. The EIS measurements indicate that the incor-
poration of TiO2, Ag, and Zn into the coating
increased both the charge transfer and the pore
resistance. The highest protection efficiency was
obtained for the PANI/Ag nanocomposite film
(PE = 97.54%). This research motivated our work to
produce the nanocomposites of PANI with Ag and ZnO,
and to develop the formulations of their synergism to
achieve balanced and improved corrosion resistance
properties for offshore or splash zone applications.14
In this study, we intend to develop a coating
containing conducting polymer (CP)-based nanocom-
posites (e.g., CP-inorganic parts and nano-pigments
such as Ag and ZnO) as a substitution for hazardous
inorganic materials such as zinc dust, zinc phosphate
(Zn3(PO4)2), and zinc chromates (Zn3CrO4) generally
used in conventional epoxy coatings. The mechanical
properties and corrosion resistance for the fabricated
coatings have been investigated using different mea-
surement methods. It was expected that the new
synthesized coatings would have good mechanical
properties and show excellent corrosion resistance in
3.5% NaCl solution.
Materials and methods
The fabricated epoxy coatings (S1–S4) were formu-
lated as reported in our previous study.1 The incorpo-
ration of Ag and ZnO nanoparticles (purchased from
Sigma-Aldrich, USA) in epoxy coating formulations
has also been applied using a mechanical mixer
followed by a sonication technique. Silane was added
to acetone and stirred for 5 min at a low rotation per
minute (rpm). Nanoparticles Ag and ZnO were mixed
into an acetone silane solution for at least 15 min to
facilitate a complete dispersion of the nanoparticles.
This prepared slurry of a silane/nanoparticle solution
was mixed with an epoxy/conducting polymer mixture
for at least 1.0 h at 4000 rpm using a mechanical stirrer.
After the mixing was complete, sonication was per-
formed for 60 min at 50C. After sonication, the
mixture was kept for stabilization for about 20 min.

After stabilization, a hardener was added to the epoxy/
CP/nanoparticle mixture, and the mixing process was
continued for at least 5–6 min at about 500 rpm using a
mechanical stirrer. This modified slurry was coated
onto various substrates for characterization using
various techniques, taking into account that the mix-
ture should be stabilized before being applied as a
coating.
Attenuated total reflectance infrared spectroscopy
(ATR-IR) measurements were used to study the
crosslinking reactions of the epoxy resin, hardener,
conducting polymer, and nanoparticles to fabricate the
coatings samples (S1–S4). For this purpose, the epoxy
coatings were formulated with a hardener and were
applied for 1 week on small glass plates. The surface
morphology of the coatings was investigated using a
field-emission scanning electron microscope (FE-SEM,
JEOL model JSM7600 F). The operating conditions for
the employed FE-SEM were 5 kV with a working
distance of 4.5 mm. The differential scanning calorime-
try (DSC) technique was conducted using a TA
Instrument SDT Q-600, which was calibrated accord-
ing to the manufacturer’s procedure (TA Instruments,
Germany). The DSC tests were conducted at a heating
rate of 10C/min from room temperature to 120C in a
nitrogen atmosphere (50 ml/min). The effects of the
nanoparticles on the mechanical properties, such as the
hardness and modulus of elasticity, were evaluated
using nano-indentation. The procedures for the nano-
indentation tests were the same as those conducted in
our previous work.1 The anticorrosive performance of
the epoxy coating system was investigated using
electrochemical impedance spectroscopy (EIS) mea-
surements in a conventional three-electrode cell, with
Ag/AgCl (in a saturated KCl solution) as the reference
electrode, stainless steel as the counter electrode, and
steel-coated coupons as the working electrode. The
area of the working electrode exposed to the test
solution (3.5% NaCl solution) was 10 cm2. The EIS
data were collected using an Autolab Ecochemie
PGSTAT 30 (Potentiostat/Galvanostat), and a fre-
quency scan within the range of 100 kHz to 1.0 mHz
was carried out by applying a ± 5 mV amplitude
sinusoidal wave perturbation at the corrosion poten-
tial.
Results and discussion
ATR-IR measurement
ATR-IR investigations were carried out to report the
dispersions of the epoxy resin, curing agent, PANI, and
distribution of Ag and ZnO nanoparticles. The aim of
using the ART-IR technique was also to characterize
the chemical compositions of the synthesized epoxy
coatings incorporating Ag and ZnO nanoparticles,
where the epoxy coatings were applied on different
glass plates and left for 7 days to be cured. The
J. Coat. Technol. Res., 16 (3) 835–845, 2019
collected ATR-IR spectra for the different fabricated
epoxy coatings incorporating nanoparticles of 0.2% Ag
(S1), 0.4% Ag (S2), 0.2% Ag + 0.2% ZnO (S3), and
0.4% Ag + 0.4% ZnO (S4) are shown in Fig. 1. These
spectra were obtained within a wide range of over
4000–500 cm1 wave numbers to cover all spectra,
which may appear for any functional groups of coat-
ings. To focus on the area of most functional groups,
ATR-IR spectra were also plotted within the range of
3500–2500 cm1, as depicted in Fig. 2.
It is well known that the combination between the
D-3282 adduct as a hardener and DGEBA as an epoxy
resin will yield various functional groups such as
aromatic rings, including –CH3, ” C–O–C ” , =C=O,
–OH, –NH2, and –N=N–. It can clearly be seen from
Fig. 1 that numerous peaks appear on the spectra,
namely 827, 1036, 1128, 1184, 1245, 1304, 1470, 1510,
1610, 1645, and 1708 cm1 and as shown in Fig. 2,
peaks at 2854, 2925, and 2962 cm1. Here, the spectra
shown in the wave number range from 700 to
1800 cm1, which proves that there are aromatic rings,
as indicated by the presence of the peaks within the
region at 1400–1000 cm1, 1510 cm1, and
1 17–22
1609 cm . Evidence of the presence of C–H
out-of-plane deformation vibration bands owing to
the ring vibrations is indicated by the appearance of
bands at 768 and 827 cm1.17–22 This is in good
agreement with a reported work18–23 in which the
chemical structure of DGEBA molecules has various
organic groups, such as –CH3, ” C–O–C ” , and
aromatic rings, whereas mixing it with PANI would
yield other groups, such as –N=N–, =C=O, –OH, and –
NH2. FTIR-ATR homogeneous peak distributions for
the different fabricated coatings revealed the presence
of all functional groups, which confirms the molecular
structure for each synthesized coating.
S4
Transmittance (%)
S3
S2
S1
4000 3400 2800 2200 1600 1000 400
Wavenumber (cm–1)
Fig. 1: ATR-IR spectra for the different fabricated epoxy
coatings incorporating nanoparticles of 0.2% Ag (S1), 0.4%
Ag (S2), 0.2% Ag + 0.2% ZnO (S3), and 0.4% Ag + 0.4% ZnO
(S4)
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FE-SEM investigations fabricated coatings show a uniform, homogeneous,

The morphology and nano-distribution on the film
surfaces were investigated using FE-SEM, the images
of which are shown in Fig. 3. It can be seen that all
S4 2963
Transmittance (%)
crack-free, and continuously close-packed structure
and highly adherent film on the substrates, which is
expected to lead to a good corrosion resistance of steel
coated with these epoxy coatings incorporated with Ag
and ZnO nanoparticles.
To confirm the composition of the fabricated coat-
ings, the percentages of the elements found on the
surface, and the distribution of these elements along

2854 with the added nanoparticles, i.e., Ag and ZnO, SEM

S3 2925
images were collected for each element individually.
2963 2854 Figure 4 shows the EDX profile and SEM images for
the distribution of Ag and C on the surface, shown in
S2 2925
Fig. 3a for the S1 epoxy coating. It can be seen from
2963 the EDX profile shown in Fig. 4 that the surface has C,
2852
Ag, and Cl, and there is no indication of the presence
S1 2921
of other elements. This confirms that the coating layer
2959 2852 is thick and completely covers the surface of the coated
2921 panel. In addition, the atomic percentages found on the
surface of the S1 coating for C, O, and Ag were
3500 3250 3000 2750 2500 80.49%, 19.36%, and 0.14%, respectively. The highest
Wavenumber (cm –1) percentage is demonstrated for C, which is expected
because the epoxy resin (DGEBA) and the curing
Fig. 2: ATR-IR spectra within the region of 3500– agent (D-3282), as well as PANI, are hydrocarbon
2500 cm21 for the different fabricated epoxy coatings compounds that have carbon as the main component in
incorporated with the nanoparticles shown in Fig. 1 their structure. The presence of O is attributed to the

Fig. 3: FE-SEM images for (a) S1, (b) S2, (c) S3, and (d) S4 epoxy coatings incorporated with Ag and ZnO nanoparticles

838

Fig. 4: EDX profile analysis and corresponding FE-SEM
images for the distribution of C and Ag taken of the surface
of S1 epoxy coating
formation of a passive layer that contains an oxide
layer on the surface of the coating. In addition, the
chloride ions (Cl-) may have deposited on the surface
of the coating, owing to the direct immersion of the
coated panels in the NaCl test solution. The percentage
of Ag (0.14%) is less than that originally present
(0.2%), which is also due to the presence of a top
passive layer on the surface of the coatings, thanks to
its immersion in the test solution for 24 h. The FE-
SEM mapping shown in Fig. 4 also confirms that C
covers the majority of the surface, and with Ag, both
are homogeneously distributed over the entire surface
of the coating.
J. Coat. Technol. Res., 16 (3) 835–845, 2019
Figure 5 shows the EDX profile analysis and corre-
sponding FE-SEM images for the distribution of O,
Ag, and Zn taken of the surface of S4 epoxy coating.
This was to report the percentage and distribution of
O, Ag, and Zn. The EDX profile (Fig. 6) reveals the
presence of C, O, Ag, and Zn; the percentages of these
components are 80.0%, 19.6%, 0.2%, and 0.4%,
respectively. Still, C represents the majority of the
elements found on the surface of the coating, whereas
the percentage of O is approximately 20%, which is
confirmed by its dense distribution, as depicted by the
FE-SEM mapping for O, as shown in Fig. 5. The
percentages of Ag and Zn are the lowest because they
were originally low (0.4%), and because of the cover-
age of the surface of the coating using a passive layer.
The homogeneous distribution of both Ag and Zn, as
shown in Fig. 6, confirms the good fabrication of the
reported nanoparticles incorporated in epoxy coatings.
The results of SEM/EDX investigations are thus in
good agreement with the results obtained from ATR-
IR spectra.
Nano-indentation analysis
The modulus and hardness properties upon incorpora-
tion of the nanoparticles were studied using the nano-
test platform from Micro Materials, UK, with a
complete software package and a Berkovich diamond
indenter. The maximum load applied for all samples
was 250 mN, and the results of 20 indentations
conducted at different locations to obtain accept-
able values of hardness (H) and elastic modulus (E)
were averaged. The hardness and elastic modulus were
calculated according to Oliver and Pharr’s24 method
through equations (1) and (2):
Fmax
H¼ ð1Þ
Ac
where H = hardness, Fmax = maximum applied, and
Ac = projected contact area.
1 1  m2 1  m2i
¼ þ ð2Þ
Er E Ei
Here, Ac is the projected contact area, and Er is the
reduced modulus. In addition, E and Ei are the elastic
modulus of the sample, and indenters m and mi are the
Poisson’s ratio of the sample and diamond indenter,
respectively.
The load–displacement curve for epoxy coatings
contains different amounts of nanoparticles and is
shown in Fig. 6. As clearly shown, at the maximum
load of 250 mN, the penetration depths are reduced.
The maximum penetration depth of 9671 nm was
recorded for the S1 sample, whereas the minimum
penetration depth was observed for S2 (8853 nm). The
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J. Coat. Technol. Res., 16 (3) 835–845, 2019

Fig. 5: EDX profile analysis and corresponding FE-SEM images for the distribution of O, Ag, and Zn taken of the surface of
S4 epoxy coating

250
S1 S2 S3 S4

Modulus of Elasticity (GPa)

200
Hardness (GPa)
LOAD (mN)

150 S2 S3 S4
S1
100

50

0.2% Ag 0.4% Ag 0.2% Ag 0.4% Ag

0
0 2000 4000 6000 8000 10,000 0.2% Zno 0.4% ZnO
DEPTH (nm) Nanoparticle (%)

Fig. 6: Load vs. displacement curves
percentages of nanoparticle loading
movement of the penetration depth to lower values
implies an improvement in the hardness values because
of an improvement in the load-bearing capacity of the
prepared coatings.25
Figure 7 shows the elastic modulus and hardness of
the studied coatings, where the improvement in the
nano-mechanical properties can be seen in Table 1, in
with different Fig. 7: Nano-indentation analysis for the fabricated
coatings, which were incorporated using 0.2% Ag (S1),
0.4% Ag (S2), 0.2% Ag + 0.2% ZnO (S3), and 0.4% Ag + 0.4%
ZnO (S4) nanoparticles
which the hardness values with the addition of an equal
proportion of nanoparticles (ZnO and Ag) are
increased. The results show an increase in elastic
modulus and hardness of the coatings from S1 to S4
because of the dual nanoparticle effect. The addition of
0.4% Ag nanoparticles provides the maximum hard-

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 J. Coat. Technol. Res., 16 (3) 835–845, 2019

Table 1: Hardness and reduced modulus recorded for the fabricated epoxy coatings containing Ag and ZnO
nanoparticles
Sample Nanoparticles Hardness (GPa) Reduced modulus (GPa)
Ag (%) ZnO (%)

S1 0.2 0.0 0.16 3.86

S2 0.4 0.0 0.18 4.30
S3 0.2 0.2 0.18 4.20
S4 0.4 0.4 0.18 4.08

Table 2: Dry film thickness, pendulum hardness, scratch resistance, and impact strength values of Ag and ZnO
incorporated epoxy coatings
Sample PANI% Nanoparticle Dry film thickness Pendulum hardness Scratch resistance Impact strength
(lm) (Kg) (in/lb)
Ag% ZnO%

S1 0.78 0.2 0.0 60–80 108 5.5 64

S2 0.78 0.4 0.0 60–80 117 6.0 72
S3 0.78 0.2 0.2 60–80 111 7.0 96
S4 0.78 0.4 0.4 60–80 100 7.5 96

7 7
5 × 10 5 × 10
(a) 1.0 × 10
6 (b)
7 7
4 × 10 4 × 10
2
–Z" / Ω cm

7 7
3 × 10 3 × 10
5
5.0 × 10

7 7
2 × 10 2 × 10

7 7
1 × 10 1 × 10 0.0
5 6
0.0 5.0 × 10 1.0 × 10

0 7 8 8
0 7 8 8
0.0 5.0 × 10 1.0 × 10 1.5 × 10 0.0 5.0 × 10 1.0 × 10 1.5 × 10
7 7
5 × 10 5 × 10
1.0 × 10
7
(c) (d)
7 7
4 × 10 4 × 10 6.0 × 10
5
2
–Z" / Ω cm

7 7
3 × 10 3 × 10 4.0 × 10
5

6
5.0 × 10
7 7
2 × 10 2 × 10 5
2.0 × 10

7 7
1 × 10 1 × 10
0.0 0.0
5 5 5
0.0 6
5.0 × 10 1.0 × 10
7 0.0 2.0 × 10 4.0 × 10 6.0 × 10
0 0
7 8 8 7 8 8
0.0 5.0 × 10 1.0 × 10 1.5 × 10 0.0 5.0 × 10 1.0 × 10 1.5 × 10
2 2
–Z' / Ω cm –Z' / Ω cm

Fig. 8: Nyquist plots obtained for (a) S1, (b) S2, (c) S3, and (d) S4 epoxy coating incorporated Ag and ZnO nanoparticles
after 24-h immersion in 3.5% NaCl solution

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J. Coat. Technol. Res., 16 (3) 835–845, 2019

6 6
1.0 × 10 1.0 × 10
(a) 5
(b)
5 5
1.0 × 10
2 8.0 × 10 8.0 × 10
Z" / Ω cm
5 5
6.0 × 10 6.0 × 10
4
5.0 × 10
5 5
4.0 × 10 4.0 × 10

5 5
2.0 × 10 2.0 × 10
0.0
5 5 5
0 1 × 10 2 × 10 3 × 10
0.0 0.0
6 6 6 6 6 6 6 6
0 1 × 10 2 × 10 3 × 10 4 × 10 0 1 × 10 2 × 10 3 × 10 4 × 10
6 6
1.0 × 10 1.0 × 10
(c) (d)
5 5 4
8.0 × 10 8.0 × 10 5 × 10
2
Z" / Ω cm

4
4 × 10
5 5
6.0 × 10 6.0 × 10
4
3 × 10

5 5 4
4.0 × 10 4.0 × 10 2 × 10

4
1 × 10
5 5
2.0 × 10 2.0 × 10
0
5 5 5
0 1 × 10 2 × 10 3 × 10
0.0 0.0
6 6 6 6 6 6 6 6
0 1 × 10 2 × 10 3 × 10 4 × 10 0 1 × 10 2 × 10 3 × 10 4 × 10
2 2
Z' / Ω cm Z' / Ω cm

Fig. 9: Nyquist plots obtained for (a) S1, (b) S2, (c) S3, and (d) S4 epoxy coating incorporated Ag and ZnO nanoparticles
after 168-h immersion in 3.5% NaCl solution

ness of 0.18 GPa and modulus of 4.30 GPa for the S2
sample, whereas the synergism of the nanoparticles at a
0.2% ratio (sample S3) provides the best values of 0.18
GPa for the hardness and 4.20 GPa for the modulus.
The obtained values of nano-indentation are in accor-
dance with conventional test results mentioned in
Table 2, where the maximum mechanical properties
were obtained for the S2 sample.
Electrochemical impedance spectroscopy (EIS)
EIS measurements have been successfully employed to
report the kinetic parameters for the electron transfer
at the surface/electrolyte interface.26–33 The Nyquist
plots obtained for (a) S1, (b) S2, (c) S3, and (d) S4
epoxy coating incorporated Ag and ZnO nanoparticles
after 24-h immersion in a 3.5% NaCl solution are
shown in Fig. 8. It can be seen that the epoxy coating
containing 0.2% Ag (S1) showed only one semicircle
with a very wide diameter. Increasing the percentage of
Ag in the coating from 0.2% (S1) to 0.4% (S2) changed
the shape of the spectrum to a small semicircle and a
long segment. The highest values for Z¢ and Z† are
shown for the S3 sample, which has 0.2% Ag and 0.2%
ZnO, indicating that the presence of Ag and ZnO at
these percentages increases the corrosion resistance of
the epoxy coating.
To shed additional light on the corrosion behavior of
the fabricated coatings after long immersion periods,
EIS measurements were carried out after 168 and
720 h, the spectra of which are shown in Figs. 9 and 10,
respectively. Figures 8 and 9 indicate that an elonga-
tion of the immersion time from 24 to 168 h decreases
the corrosion resistance through a decrease in the
values of the spectra obtained, which is most probably
due to the slight degradation of the coatings with time.
Further increasing the immersion time to 720 h before
the measurements decreased the values of both the
real and imaginary resistances through a decrease in
the diameter of the semicircles. It is believed that the
corrosion resistance of the coatings increases in the
presence of both Ag and ZnO nanoparticles, which is
obvious for the epoxy coating containing 0.2% Ag and
0.2% ZnO nanoparticles, namely S3, and 0.4% Ag and
0.4% ZnO nanoparticles, namely S4. This result comes
from a synergetic effect occurring between the epoxy
coating and Ag along with the ZnO nanoparticles, and
thus the presence of Ag and ZnO nanoparticles
strengthen the mechanical properties of the coatings
and increase the resistance against corrosion in 3.5%
NaCl solution.

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40,000 40,000
35,000 (a) 35,000 (b)
2
–Z" / Ω cm 30,000 30,000
25,000 25,000
20000 20,000
15,000 15,000
10,000 10,000
5,000 5,000
0 0
0 50,000 100,000 150,000 200,000 0 50,000 100,000 150,000 200,000
40,000t 40,000
35,000 (c) 35,000 (d)
30,000 30,000
2
–Z" / Ω cm

25,000 25,000
20,000 20,000
15,000 15,000
10,000 10,000
5,000 5,000
0 0
0 50,000 100,000 150,000 200,000 0 50,000 100,000 150,000 200,000
2 2
–Z' / Ω cm –Z' / Ω cm

Fig. 10: Nyquist plots obtained for (a) S1, (b) S2, (c) S3, and (d) S4 epoxy coating incorporated Ag and ZnO nanoparticles
after 24-h exposure in 3.5% NaCl solution

representing the polarization resistance between the

RS Q1
RP1 Q2
RP2
Fig. 11: Equivalent circuit model employed to fit the
impedance data shown in Figs. 8, 9, and 10
To quantify the effect of Ag and ZnO nanoparticles
on the corrosion resistance of epoxy coatings, the data
obtained from EIS plots for the coatings after immer-
sion for different exposure periods were best fitted to
an equivalent circuit, which is shown in Fig. 11. The
values of the impedance parameters obtained from the
fitting of the EIS data to the equivalent circuit shown in
Fig. 11 are listed in Table 3. The circuit consists of a
solution resistance (RS), constant phase elements (Q1),
polarization resistance (RP1), another constant phase
element (Q2), and a second polarization resistance
(RP2). It is clear from Table 3 that Q1 represents a
typical double-layer capacitor with significant porosi-
ties because their n1 values are close to 1. Here, RP1
can be considered as the charge transfer resistance
epoxy coatings and the solution interface, and RP2 is
the polarization resistance between a corrosion pro-
duct layer and/or an oxide film and the solution, and
the overall polarization resistance is obtained from the
parallel combination of RP1 and RP2.30,31 The Q2 values
have characteristics of a Warburg with their n2 values
at approximately 0.5, which indicates that the surface
of the fabricated coatings have high corrosion resis-
tance. The EIS data thus confirm that the accelerated
corrosion assays using an aggressive 3.5% saline
solution revealed that the panels coated with PANI-
based epoxy coatings (a synergism of Ag and ZnO
nanoparticles, S1–S4) are significantly more resistant
against corrosion than those protected with conven-
tional epoxy coatings. Moreover, epoxy nanocomposite
coatings combine the advantages of a synergism of
epoxy, polyaniline, and Ag + ZnO nanoparticles (S1–
S4). Among them, the corrosion resistance of epoxy
coating S3 recorded the highest resistance compared
with the other coatings, and was far better compared to
the conventional epoxy coatings incorporated with
polyaniline even over long periods of immersion time,
namely 168 and 720 h, in a corrosive NaCl medium.

843
J. Coat. Technol. Res., 16 (3) 835–845, 2019

Table 3: EIS parameters obtained by fitting the Nyquist plots for the epoxy coatings immersed in 3.5% NaCl
solutions for 24 h, 168 h, and 720 h, respectively
Sample Parameters
RS/X Q1 RP1/k X Q2 RP2/k X
YQ1/lF n1 YQ2/lF n2

S1-24h 476 780 0.96 23,700 252 0.51 94,300

S2-24h 473 881 0.95 80.3 140 0.28 3180
S3-24h 904 547 0.97 4160 92.3 0.39 32,300
S4-24h 675 213 0.91 73.3 104 0.38 5910
S1-168h 622 101 0.94 340 152 0.37 544
S2-168h 363 115 0.94 146 188 0.50 93.0
S3-168h 936 392 0.91 100 748 0.95 45,100
S4-168h 599 122 0.98 68.7 254 0.28 268
S1-720h 865 285 0.86 66.2 181 0.24 60.6
S2-720h 562 339 0.87 44.6 90.2 0.27 52.2
S3-720h 1090 322 0.85 88.4 105 0.28 117
S4-720h 232 308 0.91 15.2 122 0.09 63.4

Conclusions terization of Corrosion Resistant Epoxy/2Pack Coatings

Four epoxy/2pack coatings containing PANI and incor-
porated Ag and ZnO nanoparticles were manufactured.
ATR-FTIR and SEM/EDX techniques were employed
to confirm the chemical composition and surface mor-
phology for the coatings obtained. The pendulum
hardness, scratch resistance, and impact strength were
measured to report the mechanical properties along
with a nano-indentation to report the indentation
hardness and modulus of the fabricated coatings. The
corrosion behavior using EIS measurements for the
fabricated coatings in 3.5% NaCl solutions after various
immersion periods of time was also studied. It was found
that the presence of Ag and ZnO nanoparticles
improves the mechanical properties and increases the
corrosion resistance for the manufactured coatings. The
corrosion resistance recorded high values even after
prolonging the immersion time in the NaCl solution for
168 and 720 h. The increase in corrosion resistance was
due to a combination of the synergistic effect between
nanoparticles (Ag and ZnO) and PANI, along with the
epoxy resin components (DGEBA and D-3282).
Acknowledgment The authors would like to extend
their sincere appreciation to the Deanship of Scientific
Research at King Saud University for its funding of this
research through the Research Group Project No.
RGP-160.
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